Fluorescent benzazole compounds containing cyanovinylene groups



United States Patent ABSTRACT OF THE DISCLOSURE Conjugated benzoxazole,benzothiazole, and benzimidazole compounds impart brilliant fluorescentyellow to orange shades to polymeric materials when incorporated thereinin minor amounts.

This invention relates to certain novel compounds and, moreparticularly, to novel fluorescent compounds containing cyanovinylengroups and to polymeric materials which have been colored with thefluorescent compounds.

The compounds of the invention have the formula wherein A and A are thesame or difierent and each represents an o-phenylene group, Q and Q arethe same or different and each represents oxygen, sulfur, or the groupNR wherein R is hydrogen, lower alkyl or aryl, R and R each represents apphenylene group or a 2,5-thiophenediyl group, B represents acyanovinylene group, and R represents a vinylene group, a p-phenylenegroup, a 4,4-stilbenediyl group, or a 2,5-thiophenediyl' group.

As stated hereinbefore, the compounds are useful colorants for syntheticpolymeric materials such as films, fibers and other shaped articles.When the compounds are incorporated into or applied to such polymericmaterials in minor amounts, they impart brilliant fluorescent yellow Ito orange shades thereto. When the compounds are so used, they exhibitexcellent light stability even when present in the polymeric materialsin concentrations as flow as 0.02%.

The phenylene, 4,4'-stilbenediyl and 2,5-thiophenediyl groupsrepresented by A A R, R and R can be substituted or unsubstituted. 'Ihesubstituents that can be present on the phenylene or 2,5-thiophenediylare not important since the primary color of the compounds of theinvention is attributable to the conjugation of the compounds incombination With the nitrogen-containing benzoxazolyl, benzothiazolyl,or benzimidazolyl groups.

The substituted phenylene, 4,4'-stilbenediyl, and 2,5- thiophenediylgroups represented by A A R, R and R in the above general formula can befurther characterized by the formulae W on (X). (X).

and

Of)! r" t S in which each X represents a substituent and n is 1, 2, 3,

or 4 and m is l or 2. When n is 2, 3, or 4 the substituents representedby X can be the same or ditferent.

3,458,506 Patented July 29, 1969 Typical monovalent substituents which Xcan represent include a halogen atom and alkyl, aryl, substituted aryl,hydroxy, alkoxy, aryloxy, acyl, acyloxy, amino, substituted amino,quaternized ammonium, sulfo, substituted sulfonyl, sulfamyl, substitutedsulfamyl, cyano, thiocyano, thiol, carbamyl, substituted carbamyl,carbamoyloxy, and nitro groups, for example. The monovalent substituentsnamed are illustrative, and not limitative, because as noted, themonovalent substituents are not important since they do notsignificantly affect the usefulness of the compounds.

Chlorine, bromine, fluorine and iodine atoms are illustrative of thehalogen atoms represented by X. When X is alkyl it preferably has 1 to18 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl,isobutyl, npentyl, n-hexyl, n-decyl, n-dodecyl, n-hexadecyl, or noctadecyl, for example. When X is aryl or substituted aryl it ispreferably mononuclear aryl such as phenyl, methylphenyl, ethylphenyl,chlorophenyl, bromophenyl, methoxyphenyl, ethoxyphenyl or othersubstituted phenyl nuclei. However, X can also be an aryl nucleus suchas l-naphthyl or Z-naphthyl and substituted derivatives thereof, or aheterocyclic nucleus such as furyl, thienyl, etc., for example.Illustrative of the alkoxy groups represented by X are alkoxy groupshaving from 1 to 18 carbon atoms, and preferably from 1 to 4 carbonatoms, such as methoxy, ethoxy, propoxy, isopropoxy, n-butoxy,isobutoxy, n-amoxy, isoamoxy, and hexoxy, for example. Phenoxy andnaphthoxy are illustrative aryloxy groups represented by X. Formyl,acetyl, propionyl, butyryl, isobutyryl, benzoyl and naphthoyl, forexample, are illustrative of the acyl groups represented by X, Acetoxy,benzoxy, CH CH COO, CH CH CH COO, and

CH CH CH CH CH COO- for example, are illustrative of the acyloxy groupsrepresented by X. Monoalkylamino, dialkylamino, wherein the alkyl groupsare the same or different, arylamino, aralkyl-a amino, cycloalkylamino,monohydroxyalkylamino, dihydroxyalkylamino, alkoxyalkylamino and otheraliphatic amino groups, for example are illustrative of the substitutedamino groups represented by X. Normally, the alkyl, hydroxyalkyl oralkoxyalkyl groups present in such amino groups contain no more than 4carbon atoms although they can contain more.

Illustrative of the substituted sulfonyl groups represented by X arealkylsulfonyl groups having from 1 to 18 carbon atoms and preferablyfrom 1 to 4 carbon atoms such as methylsulfonyl, ethylsulfonyl,propylsulfonyl, ibutylsulfonyl, etc., and arylsulfonyl, preferablymononuclear arylsulfonyl such as phenylsultonyl, methylphenylsulfonyl,chlorophenylsulfonyl, and ethoxyphenylsulfonyl. Illustrative of thesubstituted sulfamyl groups represented by X are alkyl anddialkylsulfamyl such as N,N-dimethylsulfamyl, N,N-diethylsulfamyl,N,N-dipropylsulfamyl, N-ethylsulfamyl, N-methylsulfamyl,N-butylsulfamyl, and N-ethyl-N-butylsulfamyl; aryl and diarylsulfamylsuch as N-phenylsulfamyl, N,N-diphenylsulfamyl, N,N-diethylphenylsulfamyl, N-phenyl-N-ethylphenylsulfamyl,N,N-dibutylphenylsulfamyl and N-ethoxyphenylsulfamyl;N-alkyl-N-arylsulfamyl such as N-ethyl-N-phenylsulfamyl,N-methyl-N-(methoxyphenyl) sulfamyl and N-butyl- N-chlorophenylsulfamyl.

Illustrative of the substituted carbamyl groups represented by X arealkylcarbamyl and dialkylcarbamyl groups wherein the alkyl radicalspreferably contain from 1 to 4 carbon atoms, such as N-methylcarbamyl,N-ethylcarbamyl, N-propylcarbamyl, N-isopropylcarbarnyl, N-butylcarbamyl, N,N-dimethylcarbamyl, N,N-diethylcarbamyl,N,N-di-butylcarbamyl and N-ethyl-N-methylcarbamyl, aryl anddiarylcarbamyl such as N-phenylcarbam- 3 yl, N,N-diphenylcarbamyl,N,N-di(ethylphenyl)carbamyl and N,N-di(methoxyphenyl)carbarnyl.

X can also be a group, for example wherein Y and Z each are a hydrogenatom, an alkyl group (preferably having 1 to 4 carbon atoms), asubstituted alkyl group (preferably having no more than 4 carbon atoms),an aryl group (such as phenyl, methylphenyl, ethylphenyl, methoxyphenyl,ethoxyphenyl, chlorophenyl, or bromophenyl, for example) and acycloalkyl group (such as cyclobutyl, cyclopentyl or cyclohexyl Theterm, acyl, unless otherwise indicated, is used broadly aid includes, inaddition to acyl groups noted hereinbefore, groups such as the ureidogroup, SO X groups and groups, wherein Y and Z have the meaningpreviously assigned to them.

X can also be a fluorinated alkyl group having 1 to 18 carbon atoms.Difluoroalkyl groups having the formula -(CH CHF and trifluoroalkylgroups having the formula --(CH CF wherein p is a whole number from 1 to17 are illustrative. Higher fluorinated alkyl groups such as -(CH (CF-CF where p is 1 to 4, for example, and 12 is 1 or 2, can also bepresent. 2,2-difluoroethyl, 3,3-difluoro-n-propyl, 4,4-difluoro-n-butyl,5,5-difluoro-n-amyl, 6,6-difiuoro-n-hexyl, 2,2,2-trifiuoroethyl,3,3,3-trifluoro-n-propyl, 4,4,4-trifluoro-n-butyl,5,5,5-trifluoro-n-amyl, 6,6,6-trifluoro-n-hexyl, CH CH CF and CH CH CFCF CF are illustrative of the fluorinated alkyl groups which X can be.

X can also be an unsaturated acylic hydrocarbon a ical such as allyl,l-butenyl, 2-butenyl, 3-butenyl, l-pentenyl, 2-pentenyl, 3-pentenyl,isobutenyl and l-isopentenyl, for example.

Typical groups represented in the above general formula as as will beillustrated by the examples below.

Generally, each of the groups represented by A A R, R and R will nothave more than one substituent, i.e. where n is l. The unsubstituted orsubstituted compounds in which n is 1 can be prepared with less expensethan the more extensively substituted compounds in addition toexhibiting colors and stabilities equal to the latter.

A particularly preferred group of the compounds of the invention arethose in which A and A each represents o-phenylene or o-phenylenesubstituted with lower alkyl, e.g. methyl, ethyl, butyl; lower alkoxy,e.g. methoxy, ethoxy; halogen, e.g. chloro, bromo; cyano; or loweralkylsulfonyl, e.g. methylsulfonyl, propylsulfonyl, butylsulfonyl, Q andQ each represents oxygen; R and R each represents p-phenylene; Brepresents cyanovinylene; and R represents vinylene, p-phenylene, orp-phenylene substituted with lower alkyl or lower alkoxy.

The compounds of the invention can be prepared by techniques well knownin the art. One method that can be employed is condensing thecyanomethyl compound having the formula and A G--RCHzCN Q1 with analdehyde of the formula OHCR CHO in the presence of an inorganic ororganic base and an inert solvent wherein A Q and R are defined aboveand R is a p-phenylene group, a 4,4-stilbenediyl group, or a2,5-thiophenediyl group. Examples of such bases are the hydroxides andcarbonates of the alkali metals such as sodium hydroxide, potassiumhydroxide, lithium hydroxide and sodium and potassium carbonate. Anothermethod that can be used is the condensation of an aldehyde A1 \CRCHO Ql.with a cyanomethyl compound having the formula NCCH -R -CH CN using abasic catalyst as described above.

Symmetrical compounds wherein A and A Q and Q R and R are the same areobtained when only one compound of the formula N A c re-enter:

N A o-n-orro is employed in the condensation reaction described above.Unsymmetri'cal compounds can be prepared by isolating the intermediatecondensation product in the formula A CRC=CHR1-CH0 N A C-R-OH=(IJR -OHCN Q CN and condensing it with a different compound of the formulawherein at least one of A and A Q and Q or R and R are different.

The position of the cyano group on the cyanovinylene group representedby B determines which of the two techniques described above is employed.The cyano group is attached to the vinylene group on the carbon atomadjacent to the groups represented by R and R if the first technique isused. If the second method is used, the cyano group is attached to thecarbon atom of the vinylene group which is adjacent to the grouprepresented by R The preparation of the intermediates and the compoundsof the invention is more fully described and illustrated by thefollowing examples.

Example 1.Preparation of p-(2-benzoxazolyl) phenylacetonitrile Asolution of 30 g. (0.13 mole) of 2-(p-tolyl) benzoxazole in carbontetrachloride is treated alternately with 26.7 g. (0.15 mole) ofN-bromosuccinimide and 1.5 g. of benzoyl peroxide. The mixture is thenrefluxed and stirred on a steam bath, then evaporated to dryness. Theresidue is slurried twice with hot water, then recrystallized fromethanol to obtain 2-(ot-bromo-p-tolyl)benzoxazole, M.P. 170-17l C.

Analysis.Calcd. for C H NOBr: N, 4.86; Br, 27.74. Found: N, 4.57; Br,27.39.

A solution of 1.6 g. (0.025 mole) of potassium cyanide in 25 ml. ofwater is treated with 7.2 g. (0.025 mole) of2-(a-bromo-ptolyl)benzoxazole in 100 ml. of ethanol. The mixture isrefluxed under nitrogen for several hours. On cooling, the solutiondeposits 5 g. of p-(2-benzoxazolyl)phenylacetonitrile, M.P. 169170 C.after recrystallization from ethanol. It has the structure:

Analysis.Calcd. for C H N O: C, 76.91; H, 4.30; N, 11.96. Found: C,77.29; H, 4.61; N, 12.02.

Example 2.-Preparation of p-(5-chloro-2-benzoxazolyl) phenylacetonitrileOne-tenth molar quantities of 4-chloro-2-arninophenol and p-toluic acidare dissolved in 100 g. or" polyphosphoric acid, warmed over steam andthen heated to 240250 C. for 4 hrs. The cooled mixture is poured intowater, the solid collected and recrystallized from ethanol to obtain5-chloro-2-(p-tolyl) benzoxazole, M.P. 138139 C.

Analysis.-Calcd. for C H ClNO: C, 68.99; H, 4.14; N, 5.75. Found: C,69.06; H, 4.03; N, 5.30.

5-chloro-2-(p-tolyl)benzoxazole is treated with N-bromosuccinimide andbenzoyl peroxide as described in Example 1 to obtain2-(a-bromo-p-tolyl)-5-chlorobenzoxazole, M.P. 197-198 C. afterrecrystallization from chlorobenzene.

Analysis.-Calcd. for C H BICINO: C, 52.l2; H, 2.82. Found: C, 51.54; H,2.63.

The above a-bromo compound is converted to p-(5-chloro-2-benzoxazolyl)phenylacetonitrile by the method of Example 1,M.P. 191192 C. after recrystallization from ethanol. It has thestructure:

6 AnalysiS.Calcd. for C H ClN O: C, 67.04; H, 3.38; N, 10.43. Found: C,67.15; H, 3.50; N, 10.16.

Example 3.-Preparation of p-(6-methoxy-2- benzoxazolylphenylacetonitrile 6-methoxy-2-p-tolylbenzoxazole is prepared byreaction of 5-methoxy-2-aminophenol with one mole of p-tolyl chloride inp-dioxane followed by thermal cyclization of the resultinghydroxy-aniline at 300 C. for 3 hr., B.P. 175 C. at 1 mm.

Analysis.Calcd. for C H NO C, 75.29; H, 5.47; N, 5.85. Found: C, 75.63;H, 5.58; N, 5.72.

2-(a-brom'o-p-tolyl)-6 methoxybenzoxazole is prepared by reaction of theabove compound with N-bromosuccinimide and benzoyl peroxide as inExample 1, M.P. 129 C.

p-(6-methoxy-2-benzoxazolyl)phenylacetonitrile is prepared by treatingthe above a-bromo compound with aqueous-alcoholic potassium cyanide asin Example 1, M.P. 131 C. It has the structure Analysis.Calcd. for C H NO C, 72.71; H, 4.59. Found: C, 72.39; H, 4.66.

Example 4.-Preparation of p-(G-methylsulfonyl- 2-benzoxazolylphenylacetonitrile 6-methylsulfonyl-2-(p-tolyl)benzoxazole is made byreaction of 5-methylsulfonyl-2-arninopheno1 with p-tolyl choride inp-dioxane followed by thermal cyclization at 300 C. for 1.5 hr., M.P.186 C.

2 (a bromo p tolyl) 6 methylsulfonylbenzoxazole is prepared bybromination of the above with N- bromosuccinimide and benzoyl peroxideas described in Example 1, M.P. 218220 C. from dioxane-water,

p (6 methylsulfonyl 2 benzoxazolyl)phenylacetonitrile, M.P. 192200 C.(from ethanol), is prepared by treating the above a-bromo compound withaqueous-alcoholic potassium cyanide solution. It has the structure:

Example .5.-Preparation of p-(2-benzothiazolyl phenylacetonitrile2-(p-tolyl)benzothiazole is prepared from o-amino-benzene-thiol andp-toluic acid by the method of Hein et al. [J. Am. Chem. Soc. 79, 427(1957)].

A solution of 30 g. (0.13 mole) of 2-(p-tolyl) benzothiazole in carbontetrachloride is treated alternately with 26.7 g. (0.15 mole) ofN-bromosuccinimide and 1.5 g. of benzoyl peroxide. The mixture is thenrefluxed and stirred on a steam bath, then evaporated to dryness. Theresidue is slurried two times with hot water then recrystallized fromethanol to obtain 2-(a-bromo-p-tolyl)benzothiazole, M.P. 121-125 C.

A solution of 3.0 g. (0.01 mole) of the above a-bromo compound and 0.65g. (0.01 mole) of potassium cyanide in 50 ml. of 50% aqueous ethanol isrefluxed 4 hr. The product is filtered off and after recrystallizationfrom ethanol has M.P. 161 C. It has the structure:

Analysis.-Calcd. for C H N S: C, 71.97; H, 4.03; N, 11.19; S, 12.81.Found: C, 71.95; H, 4.38; N, 10.68; S, 12.91.

7 8 Example 6.-Preparation of p-(l-phenyl-Z- tallizations froml-chloronaphthalene the melting point benzimidazolyl)phenylacetonitrileis 421-424 C. The product, oi-bis[p-(2-benzoxazolyl)1-phenyl-2-p-tolylbenzimidazole is prepared frompphenyl]-p-benzenediacrylonitrile, has the structure tolnaldehyde andN-phenyl-o-phenylenediamine using the 10 Analysis.Calcd. for C H N O C,80.55; H, 3.91; conditions described for preparing2-p-tolylbenzimidazole N, 9.89. Found: C, 80.34; H, 4.15; N, 10.10. inU.S. Patent 3,073,841. 1-phenyl-2-p-tolylbenzimidazole is converted tothe u-bromo-p-tolyl derivative which is then converted to thecorresponding nitrile by the proce- A Solution is prepared by warming0.23 g. (0.001 mole) dure described in Example 1. The product has theformula of p-(Z-benzoxazolyl)phenylacetonitrile and 0.1 g. (0.0005 mole)of 2,5-dimethoxyterephthalaldehyde in 150 ml. of ethanol. The solutionis cooled to room temperature and II 2 drops of 50% sodium hydroxidesolution are added Q causing the immediate formation of a stronglyfluorescent I red-orange solid. Recrystallization from 1,2,4-trichlorobenzene and then l-chloronaphthalene gives the product melting at375-376 C. The product, a,a-bis[p-(2-benzoxazolyDphenyl] 2,5 dimethoxy pbenzenediacrylonitrile, has the formula Example 9 C: R6). Q

ON N

OCH: Example 7.--Preparation of 5-(2-benzoxazolyl)- Analysis.-Calcd. forC H N O C, 76.66; H, 4.18;

Z-thiopheneacetonitrile N, 8.94. Found: C, 76.37; H, 4.47; N, 8.81.

2-(S-methyl-Z-thienyl)benzoxazole is prepared by the Example 10 reactionof o-aminophenol and 5-methyl-2-thiophenecar- Amixture of 8.92 (0.04mole) of {phenzoxazol 1 boxyhc g the presence of P acld at 220 Q"benzaldehyde, 3.12 g. (0.02 mole) of :1-benzenediacet n i- 87-8752'(s'methyl'zthlenyl)benzoxazole 15 trile and 3 drops of 50% aqueoussodium hydroxide soluverted to the f' comllollnd and then to tion isheated 30 min. in refluxing ethanol. The yellow810134)'z'thwpheneacemmmle by the cmdltms 40 solid which formed isfiltered ofi, washed with hot ethanol, scnbgd m Examp 1e The product hasthe formula then recrystallized from l-chloronaphthalene to obtain theproduct with M1. 375377 C. The product, oc,oa'-p- N II I phenylebis[p (2benzoxazolyl)cmnamomtr1le], has the structure N CHaCN .N I-iI| MQ eQ QWNo N The aldehyde derivatives of the intermediates describedAnalysis.-Calcd. for C H N O C, 80.54; H, 3.92; above, i.e. thecompounds having the formula N, 9.89. Found: C, 80.35; H, 3.90; N, 9.85.

N Example 11 A solution of 8.9 g. (0.04 mole) of p-(2-benzoxazolyl)benzaldehyde and 2.1 g. 0.02 mole) of 1,4dicyano-2- butene in anhydrousethanol is treated under nitrogen with 0.23 g. (0.01 mole) of sodiumdissolved in anhydrous ethanol. The mixture is stirred overnight at roomtempera- Exam 1e 8 ture, then filtered and washed with ethanol. Theproduct,

p 1,6-bis [p-(2 benzoxazolyDphenyl] 1,3,5 hexatrien-2,5-

A solution is made by dissolving 0.47 g. (0.002 mole) dicarbonitrile, isrecrystallized from 1,2,4-trichlorobenzene ofp-(2-benzoxazolyl)phenylacetonitrile and 0.13 g. (0.001 to obtain ayellow solid, M.P. 362 C. It has the structure:

mole) of terephthalaldehyde in 100 ml. of ethanol. Two AnalysisFCalcd.for C H N O C, 79.05; H, 3.91. drops of 50% sodium hydroxide solutionare added to Found: C, 79.06; H, 4.23.

catalyze the condensation. A strongly fluorescent yellow precipitateforms immediately Which, after 15 min. at room temperature, is removedby filtration yielding 0.6 g. A mixture of 0.70 g. (0.0026 mole) ofp-(5-chloro-2- (100% of theory) of crude product. After tworecrysbenzoxazolyl)phenylacetonitrile and 0.17 g. (0.0013 mole) can beobtained by applying the well-known Sommelet reaction to the a-bromoderivatives prepared in the examples above.

Example 12 of terephthalaldehyde in ethanol is condensed as in Ex-Bis[p-[6-(methylsulfonyl) 2 benzoxazolylJphenyl] pample 8 to obtain 0.7g. of a,a'-bis[p-(5-chloro-2-benzbenzenediacrylonitrile has thestructure:

N 3 I I CN CN oxazo1yl)phenyl]-p-benzenediacrylonitrile, M.P. 435 C.Example 16.-Condensation of p-(Z-benzothiazolyl) after recrystallizationfrom l-chloronaphthalene. The phenylacetonitrile product has thestructure: Using the conditions of Example 8, 7.5 g. (0.03 mole) ofp-(2-benzothiazolyl)phenylacetonitrile and 2.0 g. (0.015

at cy gglo Analysis.Calcd. for C H N O Cl 'C, 71.81; H, mole) ofterephthalaldehyde are condensed to yield 9.0 3.18. Found: C, 71.71; H,3.40. g. of product. Extraction with hot 1,2,4-trichlorobenzene 29leaves an orange-yellow solid Which is recrystallized froml-chloronaphthalene to obtain a,u'-'biS[p-(2 benzothia- Using the Con tons f Ex pl 1-0 g. (0.0038 zolyl)phenyl]-p-benzenediacrylonitrile, M.P.403 C. It mole) of p-(6-methoxy-2-benzoxazolyl)phenylacetonitrile hasthe structure:

Example 13 1 1 =r@ ON I CN and 0.25 g. (0.0019 mole) ofterephthalaldehyde are con- Analysis.Calcd. for C H N S C, 76.22; H,3.71.

densed. The condensation products are separated by their Found: C,76.34; H, 4.07. solubility difference in hot o-dichlorobenzene. Theintermediate condensation Product, 6methoxy z 4 -(2-benzoth1azolyl)-04'-cyano-4-stilbenecarboxaldehyde'benzoxazolyl)-4-sti1'benecarboxaldehyde, is much more The above1,2,4-trichlorobenzene solution is evaporated ol eg;@lv

solu'ble than the compound a,a'-biS[p-(6 methoxy 2- to a yellow solidwhich is recrystallized from benzene to benzoxazolyl)phenyl] pbenzenediacrylonitrile. a'- tai I1 y1)-a'cyano 4 stilbenecarbox- Cyano4' (6 methoxy 2 benzoxazolyl) 4 stil- "aldehyde, M.P. 215 C.,' theintermediate condensation benecarboxaldehyde, M.P. 252254 C., isobtained by. product.

distillation of the o-dichlorobenzene solution, then re-'Analysis.Calcd. for C H N SO: C, 75.38; H, 3.86; crystallization of theresidue from benzene. The product 40 Found: C, 75.18; H, 4.05.

resulting from the complete reaction of the reactants has The use ofcquimolar amounts of substituted phenylthe structure acetonitrile andterephthalaldehyde causes 4-(2 benzo- OCH3 Example 14thiazolyl)-a'-cyano 4 stil-benecarboxaldehyde to be the The condensationof a'-cyano-4-(6-methoxy-2-benzox- Q malor Product of the condensationazolyl)-4-st1lbenecarboxaldehyde (Example 13) and p- Example l7condensing 4' (z benzothiazolyl) a,

(6 methylsulfonyl 2 'benzoxazolyl)phenylacetonitrile according to theprocedure of Example 8, yields the I product, a-[p-(6-methoxy-2benzoxazolyl)phenyl] a'- (Example 16) and p-(Zbenzoxazolyl)phenylacetoni-[p-]6-(methylsulfonyl)-2-benzoxazolyl[phenyl] p bentrile (Example 1)according to the procedure of Example zenediacrylonitrile, which has thestructure 8 gives the compound a-[p-(2-benzothiazolyl)phenyl] -ot-Example 15 [p-(2-benzoxazoly1)phenyl]-p benzenediacrylonitrile. It Asuspension of 0.16 g. (0.0005 mole) of p-(6-methylhas the structurecyano-4-s tilbeneearboxaldehyde solfonyl 2benzoxazolyl)phenylacetonitrile and 0.034 g.

(0.00025 mole) of terephthalaldehyde in ethanol is treated Example 18with one drop of 50% sodium hydroxide solution and stirred at roomtemperature for three hours. The yellow A solution of 0.48 g. (0.002mole) of p-(2-benzothiaprecipitate, M.P. 330 C., is washed withethanol.a,a'- zolyl)benzaldehyde and 0.1 6 g. (0.001 mole) of p-ben- 1 1zenediacetonitrile in 100 ml. of ethanol is treated with 2 drops of 50%sodium hydroxide solution and stirred overnight at room temperature. Theresulting yellow precipitate is recrystallized twice from1,2,4-trichlorobenzene, M.P. 355357 C. The product, a,a'-p-phenylenebis-10 [p-(2-benzothiazolyl)cinnamonitrile], has the structure:

12 benzoxazolyl)-2-thiopheneacrylonitrile]. It has the structure:

lLll gg llllj Example 22 According to the method described in Example 8,p-(lphenyl-Z-benzimidazolyl)phenylacetonitrile (Example 6) is reactedwith terephthalaldehyde to yield the compound Analysis.Calcd. for C H NS C, 76.21; H, 3.71; S, 10.71. Found: C, 76.20; H, 3.80; S. 10.76.

Example 19 Using the condensation conditions of Example 8, p-(2-benzoxazolyl)phenylacetonitrile and 2,5-thiophenedicarboxaldehyde in 2:1molar amounts yield the compound, oc,oc' bis [p- (Z-benzoxazolyl)-phenyl] 2,5 -thiophenediacrylonitrile, with the structure:

C=CHHC \Olgl s H IQ O CN CN Example 21 This condensation product isobtained using the conditions of Example 8. The condensation of-(2-benzoxazolyl)-2-thiophenecarboxaldehyde and p-benzenediacetonitrilegive the compound a,u'-p-phenylenebis[5-(2- a,a'-[(1phenyl-Z-benzimidazolyl)phenyl] -p-benzenediacrylonitrile which has thestructure:

Example 23 The condensation of p-(l-phenyl-Z-benzimidazolyl)-benzaldehyde and p-benzenediacetonitrile as described in Example 8 givesthe product a,a'-p-phenylenebis[p-(phenyl-2-benzimidazolyl)-cinnamonitrile] having the structure:

Example 24 Reacting S-(Z-benzoxazolyl) 2 thiopheneacetonitrile withterephthalaldehyde as described in Example 8 yields the orange product,a,ot'bis[S-(Z-benzoxazolyl) -2-thienyl]- p-benzenediacrylonitrile,having the structure:

Example Under the reaction conditions of Example 8, the reaction of4,4'-sti1benedicarboxaldehyde, prepared by the method of Drefahl andPlotner [Chem. Ber. 91, 1274- 3,458,506 13 14 (1958)], andp-(Z-benzoxazolyl)-phenylacetonitrile yields nitrile (0.020 g.) (Example8) is dry mixed with 100 g. the compound a,u-bis[p(2-benzoxazolyl)phenyl]-4,4'- of poly(1,4-cyclohexylenedimethyleneterephthalate) stilbenediacrylonitrile, an orange solid. It has thestrucpolyester granules. The mixture is melted at 310 C. and ture:extruded through a spinnerette in the usual manner. The

Example 26 fibers obtainedare a brillant, fluorescent yellow color. Thecondensation of 4,4 bis(cyanomethyl)stilbene, The 'hght Stabmtyexcellent prepared from 4,4-bisbromomethylstilbene [Drefahl and Example28 f l 1274.450 (1958) 1 by the method Use of poly(ethyleneterephthalate) polyester with the descnbed m Example wlthFabenzoxazolynbenz' 15 same compound under the conditions described inthe aldehyde yields the compound a,u-(4,4'- Y above example givesbrilliant, fluorescent yellow fibers.[P-(2-beI1Z0XaZ01Y1)elllnamollltrlle]- The Product has the The depth ofdyeing-and the light stability are even better formula than in Example27.

N N \O ON CN The compounds of the invention are excellent color- At0.06% concentration, the dye confers still deeper ants Shaped articlesof y of the transparent and more brilliant coloration in poly(ethyleneterephtranslucent, normally solid fiberand film-forming resins thalate).

or polymers such as fibers, films, molded articles, etc. The Example 29p compounds exhibit a strong tinctorial efiect upon such Using h ditionof Example 27, m, [P-( polymeric materials at concentrations as low as0.02%. benzoxazolynphenyl] 2,5 dimethoxy p benzenediacnh Even at 9COHFeHtIatIOHS, the compounds qlsphy 30 lonitrile (Example 9) givesbrilliant, fluorescent orange excellent tab1hty to hghtt comPounds ofthe P F fibers on melt-spinning in poly(ethylene terephthalate). tronalso impart to polymeric matenals a color which is The light stabilityis excellent fluorescent which enhances the brilliance and sheen of theE 1 30 surface of the colored article. Concentrations of the com- Xamp epounds of the invention in polymeric materials of about 3 .Uslng theeendltlens 9 p e "P1 3 0.01% to about 1.0% have been found to giveexcellent bls[p'(2'benzoxazolyl)emnamonltnle] p olor ti gives brilliant,fluorescent yellow fibers on melt-spinning Examples of the polymers inwhich the compounds of in poly(ethylene terephthalate), With eXcellentlight the invention can be incorporated to give novel composi- Y- tionsare polyolefins, e.g. polyethylene, polypropylene, Example 31polyallomer; polyesters, poly(ethylene terephthalate), Using theconditions f Example 27 POM1,4-cyclohexylenedimethylene p e), abenzoxazolyl)phenyl] 1,3,5 hexatriene 2,5 dicarbo-P013!(el-hyleflellaphihalenedlearbexyhe) IPOdIfiCaUQnS nitrile (Example11) gives brilliant, fluorescent yellow of 511011 polyesters; p y p y yl 6011mm fibers on melt-spinning in poly(ethylene terephthalate), ingvinyl chloride, vinylidene chloride and other modifiers i excellentlight i i such as N-isopropylacrylamide; polyurethanes; rayon; celluloseesters, e.g. cellulose acetate, cellulose triacetate, Example 32cellulose propionate, cellulose acetate butyrate; poly- Melt-spinninga,or'blS[p-(2 benzoxazolyl)phenyl]-pmi a, y n 6 ny nfi. ny n 8,e1a t0mri benzenediacrylonitrile (Example 8) at 0.02% concentrapolye rs, n h rfi rn filmforming materials. 5 tion in polyamide (nylon 66) sold underthe trade name The materials named are merely illustrative and not Zytel101, gives fluorescent yellow fibers.

lirnitative of the polymeric materials that can be colored The followingexamples illustrate the preparation of wlth the compounds of theinvention. films and shaped objects containing the dyes of the in- Thecompounds of the invention can be incorporated vention,

into the polymeric base materials by several techniques. For example,incorporating the compound in the polymer prior to extrusion orspinning, either directly or as a master batch, gives particularly goodresults as does incorporation during the process of polymer manufacture,such as in the preparation of polyesters.

The polymeric materials can also be colored with th compounds of theinvention by dyeing using the heat fixation technique described by T. W.Gibson et al., Thermosol Method of Dyeing, American Dyestulf Reporter42, 1 (1953).

The compounds of the invention can also be mixed with a molding powderin a conventional mixer. In the case of certain low melting polymerssuch as polyolefins, Example 34 the polymer and color compound can bemilled together on hot rolls.

The following examples will serve to illustrate the 5 Example 33a,ot'-Bis[p-(2 benzoxazolyl)phenyl]-p-benzenediacrylonitrile (Example 8)(0.5 g.) is mixed with 100 g. of poly(ethylene terephthalate) and thismixture is then blended with 900 g. of poly(ethylene terephthalate)pellets. The resulting mixture is then extruded as a film at afeeding-zone temperature of 265 C., a melt-zone temperature of 295 C.and a dye temperature of 270 C.

The film is oriented with 200% stretch (drafting and tentering) at 200F., then heat set at 220 C. The film, which contains 0.05% concentrationof the cyanovinylene compound, is a bright fluorescent yellow.

a,a'-BlS[p-(2 benzoxazolyl)phenyl]-p-benzenediacrylonitrile (Example 8)is solvent dispersed on polyester pellets (molding grade). The solventis evaporated and .chniques emPb-Yed F i Polymeric materiels shapedobjects are injection molded 550 F., 500 p.s.i.) wlth the compounds ofthe mventlon' 7 from the dried pellets. Concentrations range from 0.01%Example 27 to 0.05%. The shaped objects so prepared are clear,yelu,ot-Bis[p-(2-benxoxazolyl)phenyl]-p-benzenediacrylolow fluorescentbodies.

. Example 35 The invention has been described in considerable detailwith particular reference to certain preferred emacrylonitrile (Example8). By injection molding at 180 g and g i q 3 be f g a the 5 C. shapedarticles are obtained having bright, fluorescent 5 an Scope 0 e mven OI}as escn e a (We an as yellow coloratiom defined 1n the appended clalms.

Example 36 We clalm:

1. A compound having the formula This example illustrates a method ofintegrally incorporating the compounds of this invention into polyestersby synthesizing the polyester in the presence of the l compound ratherthan adding the dye to the already 2 formed polyester. wherein Nineteenand four tenths grams (0.1 mole) of :dl- 1 and 2 each representsOwens/lane or 01911611346116 methyltirephthalate (0-02 mole) ofsubstituted with lower alkyl, lower alkoxy, halogen, hexanedrmethanol,16 drops of a 14.4% solution of Wane. or lower alkylsulfonyl;

NaHTi(OC H9) Q Bfild Q eaghrepres ents oxygen, sulfur, or -NR inbutanol, and 8 mg. of 0:,oc' bis[p (2 benzoxazolyl) 3 55;? R representshydrogen lower alkyl or phenyl] p benzenediacrylonitrile are placed in aflask and heated with stirring to l90-200 C. The ester interl i g frepresents p Phenylene or thlo change is rapid and the temperature israpidly increased to about 270 C. The reaction is then put under reducedR1 epresents vmylene, p-phenylene; p-phenylene subpressure (about 1 mm.)and the temperature raised to stituted with lower alkyl or lower alkoxy;

300-310 C. over a 1 /2 hr. period. The viscous reaction mixture is thenlet down to atmospheric pressure with 2 352? i i iiigggggfi g edlylsubstltuted wlth nitrogen and the resulting polymer is removed. Thepolymer is a brilliant, fluorescent yellow solid with a crys- 3 2 ggzzggi gigggzgi g if 1 wherem talline melting point of 290-300 C.,inherent vis- Rand R2 each represents ppbewlenemnd cosity 0.78. E 1 37 Rrepresents p-phenylene.

xampe 3. A compound according to claim 1 having the for- A 100%polyester fabric woven from poly(ethylene mula terephthalate) fibers isdyed with 04,01. -bis[p- (2-benz- 4. A compound according to claim 1having the foroxazolyl)phenyl] p benzenediacrylonitrile using the 40mula OCH:

B represents cyanovinylene; and

heat fixation technique as described in the American Dyestulf Reporter42, 1 (1953). The dyed fabric is a fiuo- 5. A compound according toclaim 1 having the forrescent, yellow shade having excellent stabilityto light. mula (EN (EN Example 38 A 50-50 polyester-cotton fabric wovenfrom poly- 6. A compound according to claim 1 having the for- (ethyleneterephthalate) and cotton fibers is dyed accordmula @t t m t ing to thetechnique, and with the compound, described in the preceding example.This dyed fabric also is a fluo- 7. A compound according to claim 1having the forrescent, yellow shade. mula 8. A compound according toclaim 1 having the formula F' In...

OH=G -0:

ON ON References Cited UNITED STATES PATENTS 3,177,208 4/ 1965 Stilz eta1. 260---240 3,260,715 7/1966 Saunders 260240 FOREIGN PATENTS 648,67412/1964 Belgium. 1,378,455 10/1964 France.

JOHN D. RANDOLPH, Primary Examiner US. Cl. X.R.

